Amidelike derivatives of dyestuffs and process of making same



Patented Get. 22, 1940 1 UNITED, STATES PATENT v OFFICE AMIDELIKEDERIVATIVES oF DYESTUFFS AND PROCESS or MAKING SAME "No DrawinglApplication December 7, 1937,,Serial N0.- 178,612., In SwitzerlandDecember'lG,

It'has been found that' dyestufis which contain at least one aminogroupunited directly to an aromatic nucleus whose ring. system consistsof notmore than 10 carbon atoms, and which. amino group .carriesatlleast' onehydrogen atom linked to the: nitrogen atom,xcan be transformed into newconversion products-which are characterized by solubility;,.by treating.the said dyestuffs with such .acylating agents which are derivedfrom or-10 ganic acids containingmore than one salt forming group, which groupitself is selected from the group consisting of carboxyl groups andsulfonic groups. I

The dyestufi'sserving as parent materials may 5 belong to variousclasses.provided that they fulfil the conditions stated in the precedingparagraph. Thus, there may" be used mono-, disor poly-azo-dyestufls,further also other dyestuifs, such as for instance dyestuffs of theanthraquinone, triphenylmethane, azine, nitro or other series. Thesedyestuffs may be used'as such or in the form of complex metal compounds,for in-' stance in theform of chromium, copper, iron,nickel.or'cobaltfcomplexes.

Acylating'agents deriving from organic acids which contain more thanonesalt-forming group selected itself from the group consisting of carboXylgroups-and sulfonic groups, are for example halides of.aliphatic,hydroaromatic or aromatic carboxylic acids whichcontain sulfonic groupsor carboxyl groups. These groups can be transformed after the'action, ofthe acylating agents on the dye into water-soluble metal salts orammonium salt's. As examples of acylating agents deriving from organicacids which contain more the group consisting of carboxyl groups andsulionic groups, there maybe mentioned halides of polycarboxylic acids,such as for example benzene-1:3:5-tricarboxylic acid, benzenehexacarboxylic acid, and polysulfonic acids, such as for example 1:3-benzene-disulfonic acid, 1:3 G-naphthalenetrisulfonic acid; furtherthere are quite particularly suitable halides of sulfo-carboxylic acidsin which both the sulfonic group and the carboxyl group are-in= the formof their halides, and those in which only the sulfonic groups or onlythe carboxyl groups are in th'e'iorm of their halides. Examples of suchcompounds are the halides of the sulfobenzoic acids, ofthesulfonaphthoic acids, of the sulfo-acid, and the like.

The acylation can be carried out by the usual methods, such as byheating the dyestuffs: with theacylating. agents Wither without theaddition of agents ,lwhichtbind; acid; or preferably. in:the

than one salt-forming group selected itself from,

I j 10 Claims. (01. 260-173) presence of tertiary bases which form nostable reaction products with acylating agents, i. e. contain neitherOI-I nor primary or secondary amino groups nor other groups capable ofbeing acylated,

particularly pyridine, or also indifferent solvents.

groups and the polyvalent acidis treated in the tertiary base withphosphorous pentachloride or phosphorous trichloride. H a

Thezproducts of the invention are characterized, as already stated, bytheir solubility. The process permits-the conversion of insoluble orsparingly soluble dyestuffs into products which are soluble in water andcan be used for dyeing in the manner of acid dyestuffs for dyeingorprinting animal fibers or in the manner of direct dyeing dyestufis fordyeing vegetable fibres, or for dyeing artificial textiles fromregenerated cellulose in a. neutral or, feebly alkalinebath, or fordyeingleather or thelike. Iffthe parent Yrnaterial contains'besides thereactive NI-I-group one" or more hydroxy groups, these latter may alsobe acylatedduring the acylation process. These acyl groups are soloosely united, however, that they are eliminated by action of mildsaponifying agents,"whereas the acyl residues-attachedtoIthe NI-I-groupsremain unattacked.

The products obtainable according to the present process representtherefore amidelike derivatives of dyestuffs of the general formula IR1N-Rg it h in which R1 stands for the radical of a dyestuff whichcontains at least one-amino group united directly-to an .aromationucleus Whose ring system consists-oi not more than 10 carbon atoms,which amino group carries at least one hydrogen atom linked'tothenitrogen atom, .Rz'stands for an ac'yl ,radicalwh-ich contains at leastone salt forming group selected from thegroups con-sisting; ofcarboxyland sulfcnic groups, and R3 standsfor a radicalselected from the groupconsisting of hydrogen and alkyl, which productsare watersoluble powdersand valuable water-soluble dyestuffs. Among these dyestuffs those areparticularly, important wherein R stands for hydrogen and/whereinthetradical R1 stands for,an

azo-dyestuff free from hydroxyl groups and having more than oneazo-group. Such products are for example those corresponding to thefollowing formulas:

Among these products those are again particularly valuable which arederived from the linear trisazo-dyestufis. They are dark powders and dyethe fiber yellow to orange and brown tints capable of discharge, whichare characterized by their fastness to light.

The following examples illustrate the invention, the parts being byweight:

Example 1 11.2 parts of amino-azo-toluene, 100 parts of pyridine and20.7 parts of toluene-2:4-disulfochloride are heated together for 2hours at 80-90 C. until a sample dissolves clearly in water.

The pyridine is then distilled as far as possible in a vacuum and theresidue is dissolved in water and neutralized by means of dilute sodiumcarbonate solution. From the solution thus obtained the desired productis salted out with sodium chloride and is then filtered and dried. It isa brown-yellow powder soluble in water to a clear solution and dyes woolfast orange-yellow. The new dyestufi corresponds with the formula CH3SOaNa The dyestuif from 4 methylamino 3:2 dimethyl-azobenzene behaves insimilar manner and leads to a product of the formula (3H3 Cl Ha O aNa ICH3 Example 2 To a mixture produced by the reaction of 16.4 parts ofbenzoic acid 3-sulfochloride with 100 parts of pyridine there are added11.2 parts of $113 (3H3 S OaNa is a bright brownish powder soluble inwater to a yellow solution. The same product is formed if instead ofpyridine another tertiary base, for instance dimethylaniline ortripropylamine is used. The benzoic acid-sulfochloride can also bereplaced by another sulfocarboxylic acid chloride, for example that ofthe furane carboxylic acid. The condensation product then corre- 'spondswith the formula CH3 CH3 6 W N=NC NHO c-o C-SOaNa Emample3 6 parts ofthe amino-azo-dyestufl from diazotized 2-methoxy-1-aminobenzene andl-amino- 7-hydroxynaphthalene are dissolved in 85 parts of pyridine andthe solution is mixed with 10 parts of benzoic acid 3 :5-disulfochlorideand then heated at 45-50 C. during one hour. 100 parts of water are now,added, followed by 35 parts of saturated sodium carbonate solution, thepyridine is distilled with steam and the residue is' extracted with 500parts of boiling saturated sodium chloride solution. After cooling 20parts of acetic acid of per cent strength are added and the Whole isfiltered. The dyestufi' on the filter of the probable formula SOaNa ISOaNa HN Example 4 8 parts of the amino-azo-dyestuff from diazotized2-methoxy-1-aminobenzene and l-amino- 7-hydroxynaphthalene are dissolvedin 65 parts of pyridine .and to the solution there are added 6 parts oftoluene-disulfochloride, and the whole is stirred during one hour at50-55 C. 100 parts of water are then added, followed by 25 parts ofsaturated sodium carbonate solution. 200 parts of a saturated solutionof sodium chloride are added, and the pyridine is distilled with steam.The dyestufi of the formula some T 0 CH3 BN- I 6011: OH

is quantitatively precipitated in crystalline form and is filtered andwashed three times with sodium chloride solution of 6 per cent strength.When dry it is a dark red powder, the aqueous solution of which dyeswool bluish-red tints.

Example 5 6.3 parts of the ainino-azo-dyestuipirom diazotized2-methyl-4-chloro-l aminobenzene and 1-amino-7-hydroxynaphthalene arestirred-together with 75 parts of pyridine and 8.5 partsi ojtoluene-disulfochloride during one hour at '70.-.

75 C. There are then added to the mixture parts of water, 25 parts ofsaturated sodium carbonate solution and 1'70 parts of saturated sodium-,chloride solution. with steam and filtering the residue, the dyestufi onthe filter is washed twice with sodium chloride solution of 7 per centstrength and isthen a red: powder which corresponds'with the. formula.

and dyes wool orange-red tints.

Example- 6- v I 19.3 parts of the acid coupling product'frodiazotized1-amino-4-nitro-2-methylsulfone and l-amino-5-hydroxynaphthalene arestirred together with 300 parts of pyridine. Into this mixture there arestrewn 33 parts of benzoic acid meta-sulfochloride and the temperatureis raised to 9 0 C. and maintained thereat until a sample OaNa S OaNa issoluble in water. The pyridine is distilled in a vacuum, the residue istaken up with water and the condensation product of the probable formulaS O aNa After distilling the pyridine" CH3 CH3 v Example 7 10 parts oftheazo-dyestufB from diazotized Lamina-4 cinnainoyl-aminobenzene and.2-amino-8'-hydroxynaphthalene-fi-sulfonic acid (alkaline coupling) arestirred with 17.6 parts of ben- ?zoic acid 3-sulfochloride and 100 partsof pyridine for 3-4 hours at 100 C. As soon as the sample becomessoluble in acidified water, the pyridine is distilled, the residue isdissolved in water, the solution is. made alkaline with sodium carbonateand boiled for a, short time and the dyestufi of the formula v SOaNa isprecipitated by means of sodium chloride. The

dyestufi is separated from the watery, layer and dried at as Iowatemperatureas possible. Itis abrown powder soluble in water to a redsolution and dyeing lcotton red.

Example 8 1214 parts of the trisazo-dyestuff obtainable by coupling 1mol of diazotized 2-amino-naphthalene-4z8-disulfonic'acidwith 1 mol ofl-amino- 3-methylbenzene, further diazotizing and coupling' with 1 molof -1-amino-3-methylbenzene, further diazotizing and coupling with 1 molof 1 aminonaphth-alene, 9" parts of benzoic acid 3- sulfochloride and100 parts of pyridine are stirred together for about 2 hours at 90.-100C. As soon.

as thesample is' soluble in acidified water, the pyridine is distilledin 'a vacuum, the residue is dissolved in waterand the condensationproduct f h Emi i some is precipitated by sodium chloride. When dry thisproduct is a dark brown powder which dissolves in water to a brownsolution in which cotton is dyed brown fast to light. The dyeings arecharacterized by their fastness to light and dischargeability. Thereaction may also be carried out in another tertiary base which is freefrom hydroxyl groups or other groups capable of being acylated, forexample in dimethylaniline, diethylaniline or triamylamine.

Products of similar properties are obtained if insteadhofmtheabovedyestuif analogously constituted dyestuffs are used. As/examples of suchproducts there may be cited the following products I 5 S0311 CH:

CH3 CH3 These products are dark powders dissolving in water to orange tobrown solutions and dyeing 40 cotton or artificial silk from regeneratedcellulose'orange to brown tints which are characterized by theirfastness to light and dischargeability. .7 Example 9 '45 v 21 parts of1:4-di- (para-aminophenyl) -aminoanthraquinone, 66 parts of benzoic acid3-sulfochloride and 300 parts of py idine are stirred together at 90-100C. until a sample of the mix- 50 ture is soluble in acidified water. Thepyridine is now distilled and the residue Worked up as describedinExample '7. i

The dark powder thus obtained corresponds with the formula 55 someIIIEFQNH- C o-C co I SOaNa C 65 dissolves in water to a blue solutionand dyes Wool in an acid bath green-blue tints.

A brown-yellow dyestuff is the product of the formula SOsH S OaH SOgH "OCH:

com I SIOaH O CHI NH-C 0- GH: SOsH which isobtained by the action ofsulfobenzoylchloride on the saponified condensation product from 1' moldinitrochlorobenzene and 1 mol acetyl-para-phenyldiamine.

Example 10 A dyebath is prepared with 2 per cent of the dyestufi ofExample 8 and 2 per cent of calcined sodium carbonate, cotton is enteredat 60 0., the bath is heated to boiling and after hour 30 per cent ofcrystallized sodium sulfate are added' and the whole is boiled foranother half hour. The cotton is thereby dyed a brown fast to light.

Emample 11 A dyebath is prepared with 2 per cent of the dyestuff ofExample 7, viscose artificial silk is entered at 60 C., the temperatureis raised to 80-90? 0., and after hour crystallized sodium sulfate isadded and dyeing is continued at the aforesaid temperature for a furtherhour. The viscose artificial silk is dyed fast pink.

Example 12 Wool is dyed in the manner usual for dyestufis that dye inacetic acid solution with 2 per cent of the dyestuff of Example 9. Thewool is dyed fast green. 7

What we claim is:

1. Process for the manufacture of amidelike derivatives of dyestufis,consisting in treating dyestufis which contain at least one amino groupunited directly to an aromatic nucleus Whose ring system consists of notmore than 10 carbon atoms, and Which amino group carries at least onehydrogen atom linked to the nitrogen atom, in a medium consisting oftertiary bases which are free from groups capable of being acylated,

with acylating agents which are derived from such organic acids whichcontain more than one salt forming group selected from the groupconsisting of carboxyl and sulfonic groups.

2. Process for the manufacture of amidelike derivatives of dyestuffs,consisting in treating dyestuffs which contain at least one amino groupunited directly. to an aromatic nucleus whose ring system consists ofnot more than 10 carbon atoms, and which amino group carries at leastone hydrogen atom linked to the nitrogen atom, in a medium consisting oftertiary bases which are free from groups capable of being acylated,with halides of such organic acids which contain more than one saltforming group selected from the group consisting of carboxyl andsulfonic groups.

3. Process for the manufacture of amidelike derivatives of azo-dyestuffsconsisting in treating azo-dyestufis which contain at least one aminogroup united directly to an aromatic nucleus whose ring system consistsof not more than 10 carbon atoms, and which amino group carries at leastone hydrogen atom linked to the nitrogen atom, in a medium consisting oftertiary bases which are free from groups capable of being acylated,with halides of such organic acids which contain more than one saltforming group selected from the group consisting of carboxyl andsulfonic groups.

4. Process for the manufacture of amidelike derivatives ofazo-dyestufis, consisting in treating amino-azo-dyestufis which are freefrom hydroxyl groups, contain more than one azogroup and at least oneprimary amino group united to an aromatic nucleus whose ring systemconsists of not more than 10 carbon atoms, in a medium consisting oftertiary bases which are free from groups capable of being acylated,with halides of such organic acids, which contain more than one saltforming group selected from the group consisting of carboxyl andsulfonic groups.

5. Process for the manufacture of amidelike derivatives ofazo-dyestufi's, consisting in treating amino-azo-dyestufis which arefree from hydroxyl groups, contain more than one amgroup and at leastone primary amino group united to an aromatic nucleus whose ring systemconsists of not more than 10 carbon atoms, in a medium consisting ofpyridine with halides of i SOIH sulfonic group and at least one primaryamino group united to an aromatic nucleus whose ring system consists ofnot more than 10 carbon atoms, in a medium consisting of pyridine, withhalides of such sulfonic acids of benzoic acid which cona) sGNs tain atleatst one and not more than two sulfonic acid groups.

'7. The amidelike derivatives of dyestufis free from hydroxyl groups,which derivatives correspond to the formula radical selected from thegroup consisting of hydrogen and alkyl, which products are watersolublepowders and valuable dyestuffs.

8. The amidelike derivatives of aminoazo-dyestuffs free from hydroxylgroups,.which derivatives correspond to the formula in which R1represents the radical of an aminoazo-dyestufi which is free fromhydroxyl groups and carries at least one amino group united. directly toan aromatic nucleus whose ring system consists of not more than 10carbon atoms, R2 represents an acyl radical which is derived from ahalide of a benzoicacid sulfonic acid which contains at least one andnot more than two sulfonic groups, which products are dark powdersdyeing the fiber yellow to orange and brown tints.

9. The aminelike derivatives of aminoazodyestuffs free from hydroxylgroups, which derivatives correspond to the formula in which R1, R2, R3and R4 represent aromatic nuclei selected from the group consisting ofnuclei of the benzene and of the naphthalene series free from hydroxylgroups whose ring systems consist of not more than 10 carbon atoms, R5represents a phenyl radical which carries at least one and not more thantwo sulfonic acid groups, and n represents a. whole number not greaterthan two, which products are dark powders dyeing the vegetable fiberorange to brown tints which are characterized by good fastness to lightand dischargeability.

10. The amidelike dyestufi of the formula SOzH CHARLES GRAENACHER.JOSEPH GYR.

o'r'ro KAISER.

FRANZ ACKERMANN. HEINRICH BRUENGGER.

